Process for the preparation of polybutylene terephthalate

ABSTRACT

In the two stage reaction of terephthalic acid with 1,4-butanediol to produce polybutylene terephthalate in which acid and diol are first subjected to catalytic esterification/oligomerization and the resulting products are thereafter subjected to catalytic polycondensation, the co-production of tetrahydrofuran is significantly reduced by conducting the polycondensation reaction prior to completion of the esterification/oligomerization reaction.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of application Ser. No.181,275, filed Aug. 25, 1980 now U.S. Pat. No. 4,346,213.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to the field of polyesters and, moreparticularly, to processes for preparing polybutylene terephthalate bydirect esterification of terephthalic acid and 1,4-butanediol.

2. Description of the Prior Art

One route to the synthesis of polybutylene terephthalate involvescarrying out the direct catalytic esterification of terephthalic acidand 1,4-butanediol in two distinct stages: in the first stage,terephthalic acid and 1,4-butanediol are reacted in the presence ofcatalyst to form bis-hydroxybutyl terephthalate and oligomers thereofand in the second stage, the bis-hydroxybutyl terephthalate and theoligomers undergo polycondensation in the presence of catalyst toprovide product polybutylene terephthalate. The first stage isconsidered at an end when the reaction medium becomes homogeneous, i.e.,when the "clearing point" indicating the conversion of substantially allthe terephthalic acid (which is highly insoluble in the reaction medium)has been reached. In conventional practice, the second stage iscommenced (by increasing the temperature and applying a vacuum) onlyafter the clearing point of the first stage reaction has occurred.Versions of the polyesterification procedure are disclosed in U.S. Pat.Nos. 3,050,533 and 3,185,668. Such a synthesis of polybutyleneterephthalate, desirable as it may be in providing a direct route tothis commercially important resin, is subject to the major disadvantagethat terephthalic acid acts as a catalyst for the conversion of1,4-butanediol to tetrahydrofuran thereby reducing yield and increasingthe production cost of the resin. It has been proposed in U.S. Pat. No.3,936,421 to minimize tetrahydrofuran production by esterifyingterephthalic acid with 1,4-butanediol in the presence of a mixture of anorganotin compound and an organotitanium compound as catalyst. Anotherproposal to minimize tetrahydrofuran production is made in U.S. Pat. No.4,014,858 which teaches the use of a tetravalent tin catalyst having oneorgano-to-tin linkage.

Because of the foregoing disadvantage associated with the directesterification method, the principal process of manufacturingpolybutylene terephthalate remains the transesterification of a dialkylterephthalate, generally dimethyl terephthalate, with 1,4-butanediolsince less tetrahydrofuran is encountered in this procedure. However,transesterification remains an indirect route to polybutyleneterephthalate and were it not for the fact that the direct synthesisapproach produces unacceptably large quantities of tetrahydrofuran, thelatter would clearly be the process of choice.

SUMMARY OF THE INVENTION

It has now been discovered that with suitable timing of the sequence ofreactions in the two-stage direct catalytic esterification ofterephthalic acid and 1,4-butanediol to provide polybutyleneterephthalate, the synthesis of this polyester can be carried out in anotherwise conventional manner but with minimal co-production oftetrahydrofuran. In contrast to the usual case where the second stagepolycondensation reaction is begun only after the clearing point of thefirst stage esterification/oligomerization reaction has been reached, itis a critical feature of the present invention to commencepolycondensation before reaching the clearing point.

Thus, in accordance with the present invention, in the process forpreparing polybutylene terephthalate in which terephthalic acid and1,4-butanediol are reacted in a first stage at an elevated temperaturein the presence of catalyst until the clearing point of the reaction isreached, and the reaction products of the aforesaid first stage arefurther reacted in a second stage at a temperature which is higher thanthat of the first stage and at substantially less than superatmosphericpressure to distill 1,4-butanediol, in the presence of catalyst toprovide polybutylene terephthalate, the improvement is provided whichcomprises commencing the second stage reaction after a major part of theterephthalic acid has been consumed in the first stage but before theclearing point of the first stage reaction has been reached.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The term "polybutylene terephthalate" as used herein contemplatessubstantially linear polyesters comprised of units derived fromterephthalic acid and 1,4-butanediol. The aforesaid term also includescopolyesters in which up to 40 mole percent of the terephthalic acid isreplaced with one or more other copolycondensable polycarboxylic acidsand/or up to 40 mole percent of the 1,4-butanediol is replaced with oneor more other copolycondensable polyols. Examples of othercopolycondensable polycarboxylic acids include isophthalic acid, adipicacid, sebacic acid, azelaic acid, dodecane dicarboxylic acid,hexahydroterephthalic acid, phenylindanedicarboxylic acid, trimelliticacid, trimesic acid and 2,6-naphthalenedicarboxylic acid. Examples ofother copolycondensable polyols include ethylene glycol, 1,3-propyleneglycol, neopentyl glycol, pentaerythritol and 1,6-hexanediol.

Any of the catalysts heretofore employed in polyesterification processescan be used herein with good results. Especially preferred are the knownand conventional organotitanium and organotin polyesterificationcatalysts used singly or in admixture. Illustrative of usefulorganotitanium catalysts are titanium tetrabutoxide, tetramethyltitanate, ethylene glycol titanate, tetrabutylene glycol titanate,tetrabutyl titanate, tetraisopropyl titanate,tetra(2-ethylhexyl)titanate, tetraoctyl titanate and tetrastearyltitanate and partially or completely hydrolyzed and transesterifiedproducts of the foregoing. Examples of organotin catalysts which areadvantageously used herein include tetraethyl tin, triethyltinhydroxide, triphenyltin hydroxide, triisobutyltin acetate, dibutyltindiacetate, tributyltin acetate, diphenyltin dilaurate, monobutyltintrichloride, dibutyltin dichloride, tributyltin chloride,methylphenyltin oxide, dibutyltin oxide, didodecyltin oxide, dibutyltinsulfide and butylhydroxy tin oxide. Of the foregoing, titaniumtetrabutoxide and tributyltin acetate are particularly preferred.

The amounts of catalysts used herein can vary over wide limits with from0.005 to 0.5 percent by weight, and preferably, from 0.01 to 0.1 weightpercent of catalyst based on the weight of the resulting polyester beingentirely sufficient in most cases.

In the first stage reaction of 1,4-butanediol and terephthalic acid, themolar ratio of diol to acid is advantageously within the range of fromabout 1.2:1 to about 2.0:1. While the process herein contemplatesconventional conditions for the first stageesterification/oligomerization reaction, e.g., temperatures of about150° C. to about 230° C. at about atmospheric or slightly subatmosphericpressure while water and minor amounts of tetrahydrofuran are beingdistilled from the reaction medium, it is especially beneficial toreducing the amount of tetrahydrofuran produced to conduct the firststage reaction at a temperature of from about 205° C. to about 215° C.and preferably, at a temperature of from about 208° C. to about 212° C.Within this restricted range of preferred temperature, a 1,4-butanediolto terephthalic acid ratio of from about 1.5:1 to about 1.8:1 providesespecially good results. The advantage to employing such a temperaturerange for the first stage is shown in the data in Table I below:

                                      TABLE I                                     __________________________________________________________________________    Effect of the temperature on the production of                                tetrahydrofuran (THF) during the first stage                                  esterificaiton/oligomerization of 1,4-butanediol (BD)                         and terephthalic acid (TA)                                                                             moles                                                                         ester-                                               Temperature                                                                          Time  moles H.sub.2 O                                                                     moles THF                                                                           bond                                                                              moles-COOH                                                                           % con-                                                                            % BD                                  (C.°)                                                                         (hr min)                                                                            formed                                                                              formed                                                                              formed                                                                            left over                                                                            version                                                                           → THF                          __________________________________________________________________________    190°                                                                          6 hr  0.27  0.020 0.25                                                                              0.15    62 3                                     200°                                                                          6 hr  0.31  0.035 0.28                                                                              0.12    70 6                                     210°                                                                          1 hr 10 min                                                                         0.42  0.03  0.4 0      100 5                                     220°                                                                          50 min                                                                              0.48  0.09  0.4 0      100 15                                    __________________________________________________________________________     Starting concentration:                                                       TA = 0.2 mole                                                                 BD = 0.6 mole                                                                 Ti (OBu).sub.4 = 2 mole % versus TA                                      

As stated above, it is essential to the process of the invention hereinto commence the second stage polycondensation reaction before theclearing point of the first stage esterification/oligomerizationreaction has been reached. In general, the clearing point of the firststage reaction can be considered to be reached when substantially allthe terephthalic acid and 1,4-butanediol have reacted to providebishydroxybutyl terephthalate which is soluble in the reaction medium.The percentage amounts of 1,4-butanediol converted to tetrahydrofuran inknown and conventional processes which commence polycondensation onlyupon reaching the clearing point are given in the data set forth inTable II as follows:

                  TABLE II                                                        ______________________________________                                        Production of tetrahydrofuran when first                                      stage reaction is carried to completion                                       (clearing point reached)                                                                      Moles   Moles                                                        Clearing of      of    after 4 hours                                          Time     H.sub.2 O                                                                             THF   Total %   % BD                                  TA/BD  reached  formed  formed                                                                              esterification                                                                          → THF                          ______________________________________                                        1/3    1 hr 20  0.51    0.10  100       12                                    1/2.5  1 hr 40  0.48    0.08  100       16                                    1/2    1 hr 45  0.44    0.03  100       8                                     1/1.7  2 hr 30  0.42    0.02  100       6                                     ______________________________________                                         If, however, at a time prior to the clearing point of the reaction, which     is readily determined for a given reaction medium and reaction conditions     employing simple and routine testing, the conditions for the second stage     polycondensation, i.e., increased reaction temperature and vacuum, are     applied to the reaction medium, the amounts of 1,4-butanediol converted to     tetrahydrofuran will be substantially reduced (Table III, infra). For     example, the reaction conditions proper to the second stage     polycondensation reaction can be applied when from about 10 weight percent     to about 40 weight percent, and advantageously from about 20 weight     percent to about 30 weight percent, of unreacted terephthalic acid remains     in the first stage reaction medium. Such reaction conditions include     temperatures of from about 225° C. to about 270° C.,     preferably from about 235° C. to 250° C., and reduced     pressures of less than 100 mm Hg, and preferably less than 75 mm Hg.

EXAMPLES 1-10

To demonstrate the significant advantage of carrying out thepolycondensation reaction herein prior to reaching the clearing point inthe first stage reaction, a series of polymerizations were run withdifferent catalyst levels at a terephthalic acid/1,4-butanediol ratio of1/1.7. The first stage reactions in each polymerization were carried outat 210° C. After the periods indicated, a vacuum (about 60 mm Hg) wasapplied in some runs and the temperature was raised to 235° C. Thereaction apparatus was connected to a distilling apparatus and a seriesof traps cooled with liquid nitrogen. In the flask of the distillingapparatus, 1,4-butanediol was collected, and the traps contained waterand tetrahydrofuran. The results of the polymerization runs aresummarized in Table III below:

                                      TABLE III                                   __________________________________________________________________________    Effect of commencing condensation before reaching the clearing                point on production of tetrahydrofuran (TA/BD = 1/1.7,                        catalyst Bu.sub.3 SnOAc, starting temperature 210° C.)                      mole %                                                                              Vacuum      % BD → THF                                                                     melting                                             Bu.sub.3 SnOAc                                                                      and 235° C.                                                                  clearing                                                                            at clearing                                                                           point                                          Examples                                                                           versus TA                                                                           after time  time    of polymer                                     __________________________________________________________________________    1    1.5   no    1 hr 15 min                                                                         4                                                      2    1.5   30 min                                                                              no                                                           3    1.5   40 min                                                                              no                                                           4    1.5   50 min                                                                              1 hr 15 min                                                                         4       228° C.                                 5    1     no    1 hr 35 min                                                                         4                                                      6    1     1 hr  no                                                           7    1     1 hr 10 min                                                                         1 hr 35 min                                                                         4       226° C.                                 8    0.5   no    2 hr 30 min                                                                         6                                                      9    0.5   2 hrs 2 hr 35 min                                                                         6       224° C.                                 10   0.1*  1 hr 15 min                                                                         1 hr 25 min                                                                         4                                                      __________________________________________________________________________     *0.1 mole % titanium tetrabutoxide cocatalyst present.                   

As these data demonstrate, substantially less tetrahydrofuran isproduced in Examples 4, 7 and 9 than that which is provided by theconventional method of applying vacuum and increased temperature onlyafter the clearing point has been reached. Examples 1, 5 and 8demonstrate the criticality of employing a vacuum and increasedtemperature for the polycondensation reaction as the absence of theseconditions will result in a failure to obtain an acceptable polymer.Examples 2, 3 and 6 show that for the particular reaction media thereinthe periods at which polycondensation conditions were applied were tooearly to provide an acceptable polymer thus demonstrating the need forexperimentally determining the optimum time for commencing the secondstage reaction for a given case.

While the procedures herein which are exemplary of the process of thisinvention illustrate batch polymerization, it will be readilyappreciated by those skilled in the art that the process of theinvention is equally applicable with conventional modification tocontinuous polymerization as well.

What is claimed is:
 1. In the process for preparing polybutyleneterephthalate in which terephthalic acid and 1,4-butanediol are reactedin a first stage at elevated temperature in the presence ofpolyesterification catalyst until the clearing point of the reaction isreached, and the reaction products of the aforesaid first stage arefurther reacted in a second stage at a temperature which is higher thanthat of the first stage and at substantially less than superatmosphericpressure to distill 1,4-butanediol, in the presence of apolycondensation catalyst to provide polybutylene terephthalate, theimprovement is provided which comprises commencing the second stagereaction after a major part of the terephthalic acid has been consumedin the first stage but before the clearing point of the first stagereaction has been reached and when from about 10 weight percent to about40 weight percent unreacted terephthalic acid remains in the first stagereaction medium.
 2. In the process for preparing polybutyleneterephthalate in which terephthalic acid and 1,4-butanediol are reactedin a first stage at elevated temperature in the presence ofpolyesterification catalyst until the clearing point of the reaction isreached, and the reaction products of the aforesaid first stage arefurther reacted in a second stage at a temperature which is higher thanthat of the first stage and at substantially less than superatmosphericpressure to distill 1,4-butanediol, in the presence of polycondensationcatalyst to provide polybutylene terephthalate, the improvement isprovided which comprises commencing the second stage reaction after amajor part of the terephthalic acid has been consumed in the first stagebut before the clearing point of the first stage reaction has beenreached and when from about 20 weight percent to about 30 weight percentunreacted terephthalic acid remains in the first stage reaction medium.